Process for forming cyan image in light-sensitive color photographic material

ABSTRACT

A process for forming a cyan image in a light-sensitive color photographic material, characterized in that a light-sensitive color photographic material having a silver halide emulsion layer incorporated with a compound of the formula   WHEREIN A is a cyan image-forming coupler residue having an Alpha -naphthol or phenol nucleus;   IS A GROUP BONDED TO THE P-POSITION OF THE HYDROXYL GROUP OF A; and Z is an atomic group necessary for forming an indazolyl group, is exposed to light imagewise and subjected to color development, or a lightsensitive color photographic material is exposed to light imagewise and subjected to color development using a color developer incorporated with the compound of the above-mentioned formula, thereby forming a cyan image corresponding to the silver image formed in the photographic material.

United States Patent 1 1111 3,770,436

Fujiwhara et al. I 1 Nov. 6, 1973 154] PROCESS FOR FORMING CYAN IMAGETN- [57] ABSTRACT LIGHTSENSITIVE COLOR A process for forming a cyanimage in a light-sensitive PHOTOGRAPHIC MATERIAL color photographicmaterial, characterized in that a [75] Inventors; Mitsuto Fujiwhara;Ryosuke light-sensitive color photographic material having a sil-Tadaaki Koga; shunji Matsuo a" f ver halide emulsion layer incorporatedwith a com- Tokyo Japan pound of the formula g h [73] Assignee:Konishiroku Photo Industry Co., Ltd., Tokyo, Japan CL, 221 Filed: Dec.23, 1971 1211 Appl, No.2 211,469 N wherein A is a cyan image-formingcoupler residue [30] Foreign Application Priority Data having ana'naphthol Phenol c Dec. 26,1970 Japan 45/119054 CH C [52] US. Cl.96/565, 96/100 51 int. Cl G03c 7/00 [58] Field of Search 96/100, 56.5 W

[56] References Cited is a group bonded to the UNITED STATES PATENTSp-position of the hydroxyl group of A; and Z is an 2,296,306 9 1942Peterson 96/565 atomic g p necessary for forming anindazolylgroup,2,353,754 7/1944 Peterson 96/565 is exposed to light imagewise andsubjected to color de- 96/100 velopment, or a light-sensitive colorphotographic ma- 3,l48,062 9/1964 Whitmore et a]... 96/100 terialisexposed to light imagewise and subjected to 3,617,291 11/1971 Sawdey96/100 color development'using a color developer incorpo- 362074511/1971 Seymour 96/100 rated with the compound of the above-mentionedfor- 3,703,375 11/1972 Groet et al 96/100 mula thereby forming a y imagecorresponding to the silver image formed in the photographic material.

3,620,747 1l/197l Marchant Primary Examiner-J. Travis Brown AssistantExaminer-Richard L Schilling 3 Claims, 1 Drawing Figure Attorney-Waters,Roditi, Schwartz & Nissen 611g 10 Kusuaq f" N l o o Amount ofExposureflog E) PATENTEBHBY 5191s 170,4 5

M] 10 Kigsueq Amount of Exposurgflog E) PROCESS FOR FORMING CYAN IMAGEIN LIGHT-SENSITIVE COLOR PHOTOGRAPIIIC MATERIAL This invention relatesto a process for forming a cyan image in a light-sensitive colorphotographic material. More particularly, the invention is concernedwith a process for forming a cyan dye image in a lightsensitive colorphotographic material using a twoequivalent cyan dye image-formingcoupler.

A photographic process, in which a photographic material containingcouplers is exposed and then developed with a developer containing anaromatic primary amine type developing agent to form a dye image, hasalready been well known. Among the couplers used in the above process,the cyan coupler, which forms an indoaniline dye by coupling with theoxidation product of the aromatic primary amine type developing agent,is a phenol or l-naphthol derivative. In case t he 4- position of saidphenol or l-naphthol derivative has not been substituted, 4 molecules ofsilver halide is required to form 1 molecule of dye. Thus, the saidcoupler is called a four-equivalent coupler.

I-I o wever, it is also well known that a coupler, in

which the hyd r og e niri the 4-position has been subsuthe same dye asin the case of the four-equivalent'coupler. In this case, the halogenatom is released during the course of color developmentfind 1 molecl ileo fdye can be formed from 2 molecules of developed silver halide.Accordingly, the said coupler is called a twoequivalent coupler.

The two-equivalent coupler is more excellent than the four-equivalentcoupler in the following points:

1. The two-equivalent coupler is higher in coupling reactivity than theknown four-equivalent coupler. 2. The amount of silver halide requiredfor forming a definite amount of dye may be one half of the amountrequired in the case of the four-equivalent coupler, so that the costcan be reduced. 3. The emulsion layer can be made thinner, so that theresulting color image is enhanced in resolution and sharpness.

4. In the case of a multi-layered photographic mateposition of the cyancoupler (hydrogen in the coupling position) has been substituted by anindazolyl group such as This substituent has the property of beingreleased at the time of color development.

Some two-equivalent couplers tend to form color stains and have theproperty of inhibiting the development. However, the two-equivalentcouplers used in the present invention are colorless and scarcely formstains. Further, cyan dyes obtained by color development from the cyancouplers used in the present invention are not only high in fastness tolight, humidity and heat but also sharp in absorption and have anextremely desirable hue for color reproduction. Certain couplers used inthe present invention canact as the so-called DIR (developmentinhibitor-releasing type) couplers which release a substance inhibitingthe development at the time of color development,

The couplers used in the present invention are twoequivalent couplershaving the formula,

wherein, A is a residue-of a cyan image-forming coupler having ana-naphthol or phenol nucleus from which has been removed the hydrogeninthe p-position to the hy- N/ onl-I-Iydroxy-4-[2-(5-chloroindazolyl)]-N-(ndodecyl )-2-naphthamide CONHCnHas These compounds can easily be obtained by synthesizing a coloredcyan from a corresponding l-naphthol type coupler and 2-aminobenzylalcohol, and heating the colored cyan in 50 percent H 80 Typicalsynthesis examples are set forth below.

SYNTHESIS EXAMPLE 1 Synthesis of l-hydroxy-4-(2'-indazolyl)-N-[8-(2,4-

di-tert-aminophenoxy)-butyl]-2-naphthamide [Exemplified coupler (1)]:

a. Synthesis of 1-hydroxy-2-(2-hydroxymethylphenylazo)-N-[8-(2,4-di-tert-amylphenoxy)- b y limwmhami 1.2 liters of pyridine,and the mixed solution was stirred at said temperature for 2 hours. Thereaction mixture was poured into an aqueous hydrochloric acid solutionand then extracted with ethyl acetate. Subsequently, the ethyl acetatewas removed bydistillation, and the residue was recrystallized from amixture of ethyl acetate and n-hexane to obtain the desired compound,

.(2,4-di-tert-amylphenoxy)-butyl]-2- naphthamide:

50 Grams of the1-hydroxy-4-(2-hydr0xymethylphenylazo)-N-[8-(2,4-di-tert-amylphenoxy)-butyl]-2-'-naphtahamide obtained in (a) was added to 800 ml. of 50 percentsulfuric acid, and the resulting mixture was heated with stirring over awater bath (8090 C.) for 2 hours. The reaction .mixture-was poured intoice water and then extracted with ethyl acetate. Subsequently, the ethylacetate was removed by distillation, and the residue was recrystallizedfrom alcohol to obtain' the desired compound, yield 32 g., m.p..2257722799 Elementary analysis:

c(%) 111%) New Calculated 71.86 6.96 6.45 Found 71.61 7.15 6.12

I SYNTHESIS EXAMPLE 2 Synthesis of 1-hydroxy-4-[2-(5-chloroindazolyl)]-N-(n-dodecyl)-2-naphthamide [Exemplified coupler )1 a. Synthesis ofl-hydroxy-4-(2-hydroxymethyl-4-chlorophenylazo)-N-(n-dodecyl-Z-naphthamide:

Toa solution of 16 g. of Z-amino-S-chlorobenzyl alcohol in 250 ml. ofhydrochloric acid added with stirring at 0 to 5 C. a solution of 8 g. ofsodium nitrate in 50 ml. of water. This solution was dropped at 15 to 20C. into a solution of 55 g. of l-hydroxy-N-(ndOcecyD-Z-naphthamide in 1liter of pyridine, and then the mixed solution was stirred at warn"temperature for 2 hours. The reaction mixture was poured into an aqueoushydrochloric acid solution and extracted with ethyl acetate.Subsequently, the ethyl acetate was removed by distillation, and theresidue was recrystallized from methanol to obtain the desired compound,yield 50 g., m.p. l37138 C.

b. Synthesis ofl-hydroxy-4-[2'-(5-chloroindazolyl)]-N-(n-dodecyl)-2-naphthamide: .4 raof the ty xyrf rtt'tuitq y h -tchloropheHylazo rN-(ndodeeyBQ-naphthsmide ob tained in (a) was added to 600 ml. of 50 percentsulfuric acid, and the resulting mixture was heated with stirring over awater bath for 2.5 hours. Thereafter, the reaction mixture was pouredinto ice water and extracted with ethyl acetate. The ethyl acetate wasremoved by distillation, and the residue was recrystallized from alcoholto obtain the desired compound, yield 23 g.

Elementary analysis:

Found 7 1 .07

SYNTHESIS EXAMPLE 3 Synthesis of 1-hydroxy-4-'[2'-(6-aminoindazolyl)]- KN-[8-(2,4-di-tert-aminophenoxy)-butyl]-2-naphthamide [Exemplifiedcoupler (4)]:

A solution of 20 g. of 1-hydroxy-4-[2-(6-nitroimibutyl]-2-naphthamide'in500 ml. of percent acgig acid was heated with stirring at 90 to C. Tothis solution was added 7.5 g. of iron powder at an elevatedtemperature, and the resulting mixture was stirred as it was for 30minutes. Aftercooling the reaction mixture, insolubles were removedbyfiltration, and the filtrate was poured into water to depositcrystals. The crystals were recovered by filtration and thenrecrystallized from methanol to obtain thedesired compound, yield 12 g.

Elementary analysis:

W Calculated 75.2 l 7.64 9.23 75.46 7.38 9.20

Found The exemplified compound (5) is obtained by acetylating theexemplified compound (1) accord ing to an ordinary procedure. Othercompounds are obtained acous gelatin solution containing a surfaceactive agent,

and then subjected to a high speed rotary mixer or a colloid mill toform a coupler dispersion. Thereafter, the dispersion is added directlyto a silver halide photographic emulsion, which is then coated on asupport, followed by drying. Alternatively, the said dispersion is set,finely cut, freed from the low boiling solvent by water-washing or thelike means, and added to a photoa graphic emulsion, which is then coatedon a support,

followed by drying. In this case, the amount of the coupler to be addedto the photographic emulsion is preferably in the range from 10 to 300.g. per mole of silver halide, but may be varied depending on theapplication purpose of the resulting photographicmaterial.

The photographic emulsions used in the'present invention may be preparedby use of various silver halides such as silver chloride, silveriodobromide and silver chlorobromide. These emulsions may containchemical sensitizers, e.g. sulfur sensitizers, such natural sensitizeras present in gelatin, reduction sensitizers and noble metal salts.Further, the emulsions may have been incorporated with ordinaryphotographic additives such as, for example, antifoggants, stabilizers,anti-stain agents, anti-irradiation agents, physical property-improvinghigh polymer additives, hardeners and coating aids, and may contain asknown carbocyanine dye, merocyanine dye, etc. as optical sensitizers forthe emulsions.

The present invention is illustrated in detail below with reference toexamples, but it is needless'to say that the invention is not limited tothese. I. Y

EXAMPLE 1 2.0 Grams of the exemplified coupler (l) was dissolved in amixed solvent comprising 2 ml. of dibutyl phthalate and 6 ml. of ethylacetate. The resulting solution was mixed with 40 ml. of a 6 percentaqueous gelatin solution and 6 ml. of a percent aqueous solution ofAlkanol B (produced by Du Pont), and the mixed solution was subjected toordinary protect dispersion method using a colloid mill to form acoupler dispersion. This dispersion was added to a silver iodobromideemulsion containing 5 g. of silver halide particles, and then theemulsion was coated on a triacetate base and dried to prepare a sample.

For comparison, a control sample was prepared in the same manner asabove by use of a coupler identical in structure, except its having noindazolyl substituent, with the exemplified coupler (l).

The thus prepared samples were individually exposed according to anordinary procedure and then developed at 24 C. for 10 minutes with adeveloper of the following composition:

Anhydrous sodium sulfite 2. N-Ethyl-N-B-methanesulfonarnidoethyl- 53-methyl-4-aminoaniline sulfate Sodium carbonate (monohydrate) .50Sodium bromide Sodium hydroxide Sodium hexamethaphosphate Benzyl alcohol4 Pure water to make Subsequently, ordinary bleaching and fixingtreatments were effected to obtain the results as set forth in Table 1.

TABLE 1 A-max Relative Coupler (mu) D-max speed Fog Gamma Exemplifiedcoupler l according to 690 3.5 130 0.09 2.2 the present inventionControl coupler 690 2.8 100 0.1 l 2.0

As is clear from the results shown in Table l it is understood that thesample containing the exemplified coupler (1), despite its being less inemulsion fog, is more excellent in relative speed, gamma and D-max thanthe sample containing the control coupler, and

thus the exemplified coupler (1) has prominent characteristics as acoupler bearing an indazolyl 'substituent.

Further, samples prepared by using each of the exemplified couplers (5),(9) and (10) in place'of the exemplified coupler (l) were also less inemulsion fog and more excellent in relative speed, gamma and D-max thanthe sample containing the control coupler.

EXAMPLE 2 Samples were prepared in the same manner as in Example l,except that 2.0 g. of the exemplified coupler (,10) was used and theamount of silvgr iodobromide contained in the emulsion was varied to1.25 g., 2.5 g. and 5.0 g.

For comparison, control samples were prepared in the same manner asabove, except that a coupler identical in structure, except its havingno indazolyl substituent, with the exemplified coupler (10) was used insuch amounts as above. 7

These samples were exposed and then developed in the same manner as inExample 1 to obtain the results as t forth n Tablel- TABLE 2 Amount ofsilver Relative Coupler halide(g) Fog speed Gamma Exemplified coupler(l0) 5 0.l3 l35 2.3 according to the present 2.5 0.l0 1 l0 2.l invention1.25 0.08 107 2.0 Control 5 0.1 l 100 2.0 coupler 2.5 0.09 74 1.8

From Table 2, it is clear that even when the amount of silver halide isreduced to one fourth, the sample containing the exemplified coupler(10) is more excellent in characteristics than the control samplecontaining the control coupler, and thus the use of the coupleraccording to the present invention is extremely great in cost reductioneffect.

EXAMPLE 3 A silver halide emulsion containing 5 g. of silver chlo-'robromide which had been incorporated with 2.0 g. of the exemplifiedcoupler (10) was coated on a support to prepare a sample. This samplewas exposed according to an ordinary procedure and then subjected todevelopment. The developer used was identical in composition with thatused in Example 1, except that the developing agent was vaired toN-methyl-pphenylenediamine hydrochloride. After the development, thesample was sufficiently washed with water, dried and then treated undersuch conditions as shown below to obtain the results setforth in Table3.

For comparison, a control sample was prepared in the same manner asabove, except that the coupler used was a coupler identical instructure, except its having no indazolyl substitution, with theexemplified coupler (l0), and then treated in the same manner as aboveto obtain the results as shown in Table 3. Treatment conditions:

Light fastness: Carbon are lamp, 50C.

16 hrs., 32 hrs.

Humidity and heat RH 77C. 7 days,

fastness: l4 days.

TABLE 3 Light fastness Humidity and heat (fading ratio) fastness Couplcr(fading ratio) 16 hr. 32 hr. 7 days l4 days Exemplified coupler 3 7 l1Control 8 9 23 coupler Fading ratio: Fading (percent) after treating theportion where the initial density was 1.0.

identical in nucleus manna exeapimea coupler (1) (l-hydroxy-4-(2'-acetylphenylazo)-N [8-(2 ,4-di-tertamylphenoxy)-butyl]-2-naphthamide)was dissolved in a mixed solvent comprising 2 ml. of tricresyl phosphate1:3 solvent mixture of tricresylphosphate and ethyl acetate, and theresulting solution was treated in the same manner as in the case of thesample A of Example 4.

For comparison, a sample B was prepared in the same manner as above,except that 1.65 g. ofa coupler identical in structure, except itshaving no indazolyl substitution, with the exemplified coupler (3) wasused in place of the coupler mixture.

The samples A and B were exposed according to an ordinary procedure,developed with the same developer as in Example 1, and then subjected toordinary bleaching, fixing and water-washing treatments to obtain theresults shown in the accompanying drawing which is a graph showing thedensity of cyan dye to red light at each stage described herein in whichthe horizontal axis represents the amount of exposure (log E) and thevertical axis the density of dye. As seen in the drawing, the sample Ais longer in straight line portion of the characteristic curve andsomewhat lower in gamma than the sample B, but it is understood that thesample A is entirely free from such detrimental effects asdesensitization and the like, and is markedly effecand 7 ml. of ethylacetate. The resulting solution 'wasdispersed in 40 ml. of a 5 percentaqueous gelatin solution containing 4 ml. of a 5 percent aqueous sodiumn-dodecylbenzenesulfonate solution. This dispersion was added to ared-sensitive photographic emulsion containing 5 g. of silveriodobromide, which was then coated on a cellulose t'riacetate base to athickness of 5 microns and dried.

Forcomparison, a sample B was prepared in the same manner as above,except that 0.6 g. of a coupler identical in structure, except itshaving no indazolyl substitution, with the exemplified coupler (1) wasused in place of the exemplified coupler (l).

The samples A and B were subjected to the same exposure and developmentltreatmer t s as in Example 1 to obtain the results set forth in Table4..

TABLE 4 Fog I Relative speed Gamma D-max Sample A 0.10 115 1.43 3.15SZIIII [B B 0." 100 1.44 2.88

' from the results shown in Table 4, his clear that even when used inadmixture with couplers which are outside of the scope of the presentinvention, the coupler according to the present invention displaysexcellent characteristics. Accordingly, when the coupler according tothe present invention is used in admixture with couplers which areoutside of the scope of the present invention, the resultingphotographic material can be controlled in speed, D-max and the likecharacteristics by merely varying the mixing ratio of the coupiers,without varying the size or amount of silver halide particles.

' EXAMPLE 5 A sample A was prepared in such a mannerthat a couplermixture composed of 0.20 g. of the exemplified coupler (3) and 1.50 g.of a coupler identical in structure, except its having no indazolylsubstitution, with the exemplied coupler (3) was dissolved in 10 ml. ofa tive as a socalled DIR (development inhibitor-releasing type) coupler.

What we claim is:

1. A process for forming a cyan image in a lightsensitive colorphotographic material, characterizedin that a light-sensitive colorphotographic material having a silver halide emulsion layer incorporatedwith a compound of the formula my wherein A is a cyanimage-forming-coupler residue having an q-naphthol or phenol nucleus;

is a group bonded to the p-position of the hydroxyl group of A; and Z isan atomic group necessary for forming an indazolyl group, is exposed tolight image wise and subjected to color development, or a lightsensitivecolor photographic material is exposed to light imagewise and subjectedto color development using a color developer incorporated with thecompound, of the abovementioned formula, thereby forming a cyan imagecorresponding to the silver image formed in the photographic material.

2. A process for forming a cyan image in a lightsensitive colorphotographic material as claimed. in claim 1, wherein said compound isrepresented by the formula CONHR

2. A process for forming a cyan image in a light-sensitive colorphotographic material as claimed in claim 1, wherein said compound isrepresented by the formula
 3. A process for forming a cyan image in alight-sensitive color photographic material as claimed in claim 1,wherein said compound is selected from the group consisting of:1-hydroxy-4-(2''-indazolyl)-N-( delta(2,4-di-tert-amylphenoxy)-butyl)-2-naphthamide;1-hydroxy-4-(2''-(5-chloroindazolyl))-N-(n-dodecyl)-2-naphthamide;1-hydroxy-4-(2''-(6-nitroindazolyl))-N-( delta(2,4-di-tert-amylphenoxy)-butyl)-2-naphthamide;1-hydroxy-4-(2''-(6-aminoindazolyl))-N-( delta(2,4-di-tert-amylphenoxy)-butyl)-2-naphthamide;1-hydroxy-4-(2''-(6-acetaminoindazolyl))-N-( delta(2,4-di-tert-amylphenoxy)-butyl)-2-naphthamide;1-hydroxy-4-(2''-(6-chloroindazolyl))-4''-(4-tert-butylphenoxy)-2-naphthanilide;1-hydroxy-4-(2''-(6-nitroindazolyl))-N-(n-dodecyl)-2-naphthamide;1-hydroxy-4-(2''-(5-chloroindazolyl))-N-(2''-ethylhexyl)-naphthamide;1-hydroxy-4-(2''-indazolyl)-4''-(4-tert-butylphenoxy)-2-naphthanilideand 1-hydroxy-4-(2''-indazolyl)-N-(n-octadecyl)-2-naphthamide.